A melt extruding process comprising a trioxane monomer and a polymeric binder

ABSTRACT

A filament and film forming process in which a monomer stream comprising at least 50 percent trioxane and a polymeric binder of either polyvinylacetate or polyacetaldehyde is melt extruded; solidified by cooling; and the trioxane polymerized in the presence of a gasiform polymerization catalyst.

ljnited States Patent Jamison Aug. 1, 1972 [54] A MELT EXTRUDING PROCESS COMPRISING A TRIOXANE [56] References Cited MONOMER AND A POLYMERIC BINDER UNITED STATES PATENTS [72] Inventor; Saunders Eliot Jamison, Summit 2,437,263 3/1948 Manning ..264/ 176 2,844,561 7/1958 Bechtold et a1 ..260/45.5 2,989,511 6/1961 Schnitzer ..260/340 [73] Asslgnee- S g jf Amen, 3,027,352 3/1962 Walling et a1 ..260/67 or 3 3,242,244 3/1966 Maly ..264/176 [22] Filed: Oct. 2, 1969 Primary Examiner-Donald J. Arnold [21] Appl' 863767 Attorney-T. J Morgan, L. I. Grim and R. A. Lucey Related US. Application Data [60] Continuation of Ser. No. 508,885, Oct. 20, [57] ABSTRACT 1965, abandoned, Division of Ser. No. 62,534, A filament and film forming process in which a OC 1960, monomer stream comprising at least 50 percent trioxane and a polymeric binder of either polyvinylacetate U-S- Cl. or polyacetaldehyde is melt extruded; 264/211 cooling; and the trioxane polymerized in the presence [51] Int. Cl. ..B28b 3/20 f a if polymerization catalyst [58] Field of Search ,.264/l76, 184, 183, 194, 212,

A MELT EXTRUDING PROCESS COMPRISING A TRIOXANE MONOMER AND A POLYMERIC BINDER This application is a continuation of Ser. No. 508,885 filed Oct. 20, 1965 now abandoned, which is a divisional application of Ser. No. 62,534 filed Oct. 14, 1960, now US. Pat. No. 3,234,543.

This invention relates to shaped, self-supporting structures extended in no more than two dimensions and to processes for making such structures from solidifiable monomers.

Synthetic fibrous materials are commonly prepared by the extrusion of a resinous material through a spinning orifice followed by solidification of the extruded stream by cooling, evaporation or coagulation. Synthetic films may be similarly prepared except that extrusion is through a die slit rather than a spinning orifice. Some resinous materials, however, are not readily extrudable except at relatively high temperatures and tend to degrade at such temperatures.

It is an object of the present invention to produce fibrous material or self-supporting films by a process which avoids thermal degradation of the fiber or film forming polymer. Other objects will appear hereafter.

The object of this invention is achieved by a process for the formation of shaped, self-supporting structures extended in no more than two dimensions which comprises polymerizing a solid phase monomer in the form of said shaped, self-supporting structure in the presence of a fluid catalyst.

This invention is particularly applicable to the polymerization of trioxane and for convenience will be described with reference thereto.

In a preferred embodiment of this invention, trioxane is admixed uniformly with a resinous binder, extruded through a spinning orifice to form a stream and then polymerized in the presence of gasiform boron fluoride after solidification of the stream. Solidification of the stream to a self-supporting structure makes the invention applicable to monomers which cannot be polymerized instantaneously.

The resinous binder serves the dual function of increasing the viscosity of the trioxane to permit it to be extruded in a fine stream and of maintaining the trioxane in a fibrous structure while polymerization takes place.

In most cases, it is desired to eliminate the resinous binder after polymerization is complete so that the fibrous residue will have the character of the oxymethylene polymer. This may be achieved by the selection of a resinous binder which is selectively soluble in a liquid solvent which is relatively ineffective as a solvent for the oxymethylene polymer. Or it may be achieved by the selection of a resinous binder which depolymerizes under the trioxane polymerization conditions so that it disappears after lending its structure to the polymerization process.

When an oxymethylene polymer fiber is desired, the resinous binder is blended with trioxane in proportions between about and 50 weight percent, based on the weight of trioxane. The binder is preferably dissolved in molten trioxane before extrusion thereof through the spinning orifice. If desired, both the trioxane and the binder may be dissolved in a common solvent to form a viscous solution and the solution may be extruded through the spinning orifice.

Solidification of the extruded stream is by cooling in the case where no solvent is used and usually by cooling and evaporation where a solvent is used. Volatile solvents and mild evaporative conditions are used with trioxane to control the trioxane loss which would otherwise occur because of the high volatility of the trioxane.

In some cases wet spinning methods may be used wherein the solution is extruded into a non-solvent liquid, such as n-octane, as a coagulant. In such cases the filaments may be polymerized in the presence of a liquid phase catalyst, such as boron trifiuoride in solution in the coagulant liquid. Alternatively, the filaments may be removed from their liquid coagulant environment before polymerization in the presence of a gasiform catalyst takes place.

Suitable resinous binders for trioxane include thermoplastic vinyl polymers such as polyvinyl acetate, polystyrene, polyvinyl chloride, polymethyl methacrylate, polyvinyl pyrrolidone, polyethyl acrylate and polyvinyl caprolactam; thermoplastic condensation polymers, such as relatively low melting polyamides,

and polyesters; and thermoplastic cellulosic derivatives, such as cellulose acetate and ethyl cellulose.

Polyacetaldehyde, prepared by acid-catalyzed polymerization of acetaldehyde at its freezing point and of the formula is a useful binder since it depolymerizes readily when exposed to a trioxane polymerization catalyst under polymerization conditions.

The nature of the common solvents used when dry spinning is desired is dependent on the nature of the resinous binder. For many binders trioxane solvents such as methylene chloride or acetone are suitable. Suitable spinning compositions of this type include from 10 to I00 weight percent of binder and from 50 to 500 weight percent of solvent per unit weight of trioxane.

Spinning conditions depend upon the nature and proportion of the resinous binder and the nature and proportion of solvent if any. The spinning orifice diameter may vary as desired according to the product desired. Spinning temperatures from about 0C. to about C. are suitable for most spinning compositrons.

After the extrusion operation is completed, the extruded stream is solidified, preferably by cooling or by cooling and evaporation. The atmosphere into which the spinning composition is extruded is preferably maintained at a temperature between about 50 and 50C.

The preferred gasiform catalyst is boron trifiuoride. It is preferably maintained in the atmosphere surrounding the solidified trioxane-binder filament at a concentration of from about 1 to 100 weight percent. Vaporizable acidic boron trifiuoride complexes may also be used. A suitable catalyst environment may be maintained by passing nitrogen through a normally liquid boron trifiuoride complex and thereafter into the polymerization zone.

Suitable liquid phase catalysts include solutions of boron trifluoride or of acidic complexes of boron trifluoride is liquids, which are non-solvents for the trioxane and resinous binder under the polymerization conditions.

Polymerization temperatures are suitably between about 50 and 60C. and the period of reaction may vary from about 12 hours to l minute. In most cases the catalytic environment is maintained just beyond the spinning orifice so that polymerization proceeds as soon as the extruded stream is solidified to a self-supporting structure. It is possible that polymerization is initiated to a minor extent before solidification but by far the greater portion of the trioxane solidifies before being polymerized.

In some cases, it may be desirable to prepare filamentary material having characteristics intermediate between those of the oxymethylene polymer and those of the resinous binder. In such cases the resinous binder is not removed after polymerization and the amount used depends upon the desired characteristics of the final product.

In another advantageous aspect of this invention a cross-linked polymeric structure may be prepared by the copolymerization of trioxane with a polyfunctional comonomer and particularly a polycyclic ether, such as a polyepoxide. This invention permits the utilization of such cross-linked copolymers since a useful filamentary material is produced by the polymerization reaction and there is no necessity for further shaping of the intractable polymer.

Among the suitable polyepoxides which may be used are the diepoxides of hydrocarbon dienes, such as vinyl cyclohexene dioxide and dicylcopentadiene dioxide; and diepoxides of substituted hydrocarbon dienes, such as 3,4-epoxy6-methylcyclohexylmethyl 3,4-epoxy-6- methylcyclohexanecarboxylate. Polymeric epoxides, such as the epoxy resins produced by the reaction of epichlorohydrin with a bisphenol may also be copolymerized with trioxane by the method of this invention. Other polycyclic ethers include diketals and diacetals of pentaerythritol and dioxetanes formed from pentaerythritol and its derivatives. It may be noted that polyvinyl pyrrolidone and polyvinyl caporlactam, mentioned above as resinous binders are also polyfunctional comonomers capable of interaction with trioxane in a copolymerization.

The polycyclic ethers are suitably blended into the spinning compositions in proportions between about 10 and 50 weight per cent, based on the weight of trioxane. Spinning and polymerization conditions are as described above.

In the copolymerization reaction, trioxane rings open to produce short chains of three oxymethylene units and the epoxy rings open to produce substituted oxyethylene units. These units. link up to form a space polymer comprising chains of oxymethylene units interspersed with oxyethylene units said chain being cross linked across carbon atoms of said oxyethylene units.

While the invention has been described with respect to the polymerization of spun structures, it is to be understood that other fibrous structures may be polymerized. For example, filaments may be prepared by drawing the viscous mixture from a softened and sticky melt thereof. Fibrous trioxane strands may also be prepared by sublimation under carefully controlled conditions, as described below in example I. While it is preferred to polymerize filamentary monomer other fibrous forms of monomer may be polymerized. Fibrous monomers having an extended dimension or at least I00 times the other two dimensions are suitable. Similarly monomers in film structures wherein each extended dimension is at least times the thickness are suitable.

If desired, the trioxane may be copolymerized with from 0.4 to 40 weight percent of ethylene oxide or dioxolane. Such copolymers have greater thermal stability than homopolymers. Since the shaping of the polymer after its formation is not required, in accordance with this invention, high thermal stability is often not essential. But where it is desired such copolymers may be prepared by forming filaments from a mixture of trioxane, comonomer and binder and polymerizing as described above.

While the invention has been described with reference to the polymerization of trioxane, the general technique is also applicable to other normally solid or solidifiable monomers. The technique is particularly applicable to cationically catalyzed vinyl monomers and to cyclic compounds in which at least one ring bond is highly polarizable because of the presence of an electronegative heteroatom. Examples of the cyclic compounds include other cyclic ethers, lactones, acetals, ketals, sulfides, imines and lactams. Examples of vinyl monomers include olefins, cycloolefins, vinyl ethers and acrylic acid derivatives. It is preferred that the monomer have a molecular weight not higher than about 300.

EXAMPLE I A fibrous sublimate of trioxane was prepared by a sequence of two condensation operations. In the first, molten trioxane was heated in a vessel covered with a watch-glass in such a manner that the trioxane vaporized in the vessel and condensed as a closely packed snow on the under surface (convex) of the watch glass. The temperature of the watch glass could not rise above the melting point of trioxane (64C.) for the condensation. The watch glass was cooled, by directing a cool air stream on the upper (concave) surface of the watch glass. Satisfactory rates of collection were maintained without boiling the trioxane (heating range 80-l 10C).

In the second condensation the watch glass with the trioxane snow attached to its lower (convex) surface was placed over another vessel which was kept cool (room temperature). A stream of warm air (5 560C) was directed at the upper (concave) surface of the watch glass so as to heat the trioxane without melting it. The trioxane then sublimed downward into the vessel where it formed a voluminous fibrous network.

A portion of the above-described fibrous mass was inserted into a stoppered test tube and sufficient boron trifluoride to provide a concentration in the test tube of 3 volume percent was thereafter introduced. The tube was maintained at 25C. for a period of minutes. The contents of the tube were then washed with acetone to remove unreacted trioxane and boron trifluoride. The polyoxymethylene fibers corresponded EXAMPLE II A 25 percent solution of polyvinyl acetate in trioxane was extruded at 90C. through a 2.0 mm orifice into a chamber held at -50C. from which it was taken up at room temperature on glass tube. The filaments thus prepared were exposed for 30 minutes in a test tube at room temperature to an atmosphere of dry nitrogen containing about volume percent of boron trifluoride. After exposure the filament was washed extensively with warm water to remove unreacted trioxane. Analysis showed that the filament had a composition of 47 percent polyoxymethylene and 53 percent polyvinyl acetate.

EXAMPLE III Polyacetaldehyde was obtained by polymerizing acetaldehyde at its freezing point (l23.5C.). Acetaldehyde (392 parts by weight) was distilled, into a cold trap maintained at its freezing point and containing 0.22 parts of boric acid. Upon completion of the distillation, 1.45 parts of polymer was recovered having an inherent viscosity of 3.0 (0.1 percent solution in acetone at C.).

Strands were drawn with a glass rod from a 10 percent solution of this polyacetaldehyde in trioxane. The strands were exposed at room temperature for minutes to an atmosphere of 100 volume percent of boron trifluoride. After washing with water, analysis showed that the polymer filaments were pure polyoxymethylene.

EXAMPLE IV Example Volume Diepoxide Wt. Oxymethylene in Copolymer IV Vinyl cyclohexene dioxide 13 45 V Vinyl cyclohexene dioxide 27 46 VI Vinyl cyclohexene dioxide [00 42 VII Dicyclopentadiene dioxide 27 52 VIII Dicyclopentadiene dioxide I00 55 IX (a) 13 49 X 27 48 XI (a) I00 49 (a) 3,4-epoxy-o-methyl-cyclohexylenethyl-3,4-ep0xy-6-methylcyclohexanecarboxylate.

It is to be understood that the foregoing detailed description is given merely by way of illustration and that many variations may be made therein without departing from the spirit of my invention.

Having described my invention, what I desire to secure by Letters Patent is:

e embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process for the formation of a shaped self-supporting structure selected from the group consisting of filaments and film which comprises melt extruding a solid phase monomer stream comprising at least 50 percent trioxane and a polymeric binder selected from the group consisting of polyvinyl acetate and polyacetaldehyde, solidifying said steam by cooling, and polymerizing said trioxane in the presence of gasiform polymerization catalyst for said trioxane wherein said catalyst is boron trifluoride or a vaporizable acidic boron trifluoride complex.

2. The process of claim 1 wherein said gasiform trioxane catalyst is gaseous boron trifluoride.

3. The process of claim 2 wherein said polymeric binder is polyvinylacetate and wherein said stream also contains between about 10 and 50 weight percent, based on the weight of trioxane of a diepoxide selected from the group consisting of vinyl cyclohexene dioxide, dicyclopentadiene dioxide and 3,4-epoxy-6-methylcyclohexylenethyl-3,4-epoxy-6-methyl cyclohexanecarboxylate.

4. The process of claim 2 wherein said polymeric binder is polyacetaldehyde and wherein said stream also contains between about 10 and 50 weight percent, based on the weight of trioxane of a diepoxide selected from the group consisting of vinyl cyclohexane dioxide dicyclopentadiene dioxide and 3,4-epoxy-6-methylcyclohexylenethyl-3,4-epoxy-6-methyl-cyclohexanecarboxylate.

Ui'lTED STATTS PATENT OFFICE CERT; ERICA e 11, OF CORRLC KOP 3,681,488 Dated Auqust 1. 1922 Invencor(s) Saunders Eliot Jamison ified that: error appears in the above-identified patent ett e and that said ers Patent are hereby corrected as shown below:

In claim 1, line 7' after, "cooling" insert the words in an atmosphere between 50C. and 50C In claim 1, line 8, after the word "trioxane" insert the words between about 50C. and 60C.

Signed and sealed this 2nd day of January 1973.

SEAL) :test; I|

IWARD M.FLETCHER,JR. ROBERT GOTJTSCHALK :testing Officer Commissioner of Patents 

2. The process of claim 1 wherein said gasiform trioxane catalyst is gaseous boron trifluoride.
 3. The process of claim 2 wherein said polymeric binder is polyvinylacetate and wherein said stream also contains between about 10 and 50 weight percent, based on the weight of trioxane of a diepoxide selected from the group consisting of vinyl cyclohexene dioxide, dicyclopentadiene dioxide and 3,4-epoxy-6-methyl-cyclohexylenethyl-3,4-epoxy-6-methyl cyclohexanecarboxylate.
 4. The process of claim 2 wherein said polymeric binder is polyacetaldehyde and wherein said stream also contains between about 10 and 50 weight percent, based on the weight of trioxane of a diepoxide selected from the group consisting of vinyl cyclohexane dioxide dicyclopentadiene dioxide and 3,4-epoxy-6-methyl-cyclohexylenethyl-3,4-epoxy-6-methyl -cyclohexanecarboxylate. 